EP2149624B1 - Élément revêtu de film multicouches et son procédé de production - Google Patents

Élément revêtu de film multicouches et son procédé de production Download PDF

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EP2149624B1
EP2149624B1 EP09159721A EP09159721A EP2149624B1 EP 2149624 B1 EP2149624 B1 EP 2149624B1 EP 09159721 A EP09159721 A EP 09159721A EP 09159721 A EP09159721 A EP 09159721A EP 2149624 B1 EP2149624 B1 EP 2149624B1
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Prior art keywords
film
hard coating
coating film
composition hard
composition
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German (de)
English (en)
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EP2149624A1 (fr
Inventor
Jörg Dr. Vetter
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Oerlikon Metaplas GmbH
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Sulzer Metaplas GmbH
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
    • C23C28/42—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by the composition of the alternating layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less

Definitions

  • the present invention relates to a multilayer film-coated member fabricated by forming a multilayer film on a substrate for abrasion-resistant members for cutting tools, molds and combustion engines or for members requiring heat resistance and abrasion resistance for airplanes, ground turbines, engines, gaskets, gears, pistons and others, and relates to a method for producing it.
  • Patent Reference 1 For the purpose of improving the heat resistance and abrasion resistance of coating films, development of various coating films is being promoted. With reference to typical cases of Patent References 1 to 3, described is one example of a process of development of coating films essentially for the purpose of improving the heat resistance and abrasion resistance of coating films. For the purpose of improving the heat resistance, many trials to coat heat-resistant materials have heretofore been made. For example, in Patent Reference 1, proposed is a coating film with oxides of Y and Si dispersed in a glassy matrix comprising SiO 2 and B 2 O 3 . This is an invention of a heat-resistant coating film with Si. However, the abrasion resistance of the film is not improved, and therefore it is difficult to apply the film to tools and slide members.
  • Patent Reference 2 proposed is a (TiAl(SiC))N coating film formed by the use of a target material with SiC powder having excellent heat resistance and abrasion resistance, for the purpose of improving the heat resistance and the abrasion resistance of TiAlN coating films widely used in the market. Accordingly, as compared with a TiAlN coating film, the (TiAl(SiC))N coating film has improved heat resistance and abrasion resistance, but since the base of the film is TiAlN, the effect of the improvement is limited. For further improving the abrasion resistance and the heat resistance, a Si (BCN) -based coating film was proposed and described in Patent Reference 3.
  • Patent Reference 1 JP-A 2002-87896
  • Patent Reference 2 Japanese Patent 3370291
  • Patent Reference 3 JP-A 2007-126714
  • the applicant of the present invention has proposed a coating film having excellent abrasion resistance and heat resistance as in Patent Reference 3.
  • a cutting tool with the coating film was tested and evaluated for its cutting capability, which confirmed more excellent performance of the tool over conventional cases.
  • the adhesion strength of the coating film must be more improved.
  • An object of the present invention is to provide a multilayer film-coated member which has both sufficient heat resistance and sufficient abrasion resistance and which has excellent coating film adhesion strength so that it can sufficiently exhibit the capability of the coating film even in cutting environments that may be more and more severe.
  • the invention relates to a method for producing the coating, according to claim 14, and to products having the claimed coating, according to claim 15.
  • the ratio of the peak area X of B-O to the peak area Y of B-N, X/Y, as obtained from the peak separation of the 1s orbit of B in X-ray photoelectric spectrometry may be X/Y ⁇ 0.2, within a range of at least 500 nm from the interface of the first composition hard coating film that is in contact with the underlying layer toward the surface of the first composition hard coating film.
  • the oxygen distribution control in a specific region of the hard coating film remarkably improves the adhesion strength of the hard coating film having both excellent heat resistance and excellent abrasion resistance.
  • Fig. 1 shows a partial constructional example of a multilayer film-coated member having two hard coating films of the invention.
  • a multilayer film-coating member 1 comprises a second composition hard coating film 3 and a first composition hard coating film 4 laminated in that order on a substrate 2 of a cutting tool or an abrasion-resistant member.
  • the above-mentioned “range of at least 500 nm from the interface of the first composition hard coating film that is in contact with the underlying layer toward the surface of the first composition hard coating film” is described with reference to Fig. 1 .
  • the underlying layer is the layer that is in contact with the first composition hard coating film, and in the case of Fig. 1 , this is the second composition hard coating film 3.
  • an interlayer may be provided between the second composition hard coating film and the first composition hard coating film; and in such a case, the underlying layer is the interlayer that is in contact with the first composition hard coating film.
  • the interface is that between the first composition hard coating film and the underlying layer, and this is the area indicated by 6 in Fig. 1 .
  • the "range of at least 500 nm from the interface toward the surface of the first composition hard coating film" is the range indicated by 5 in Fig. 1 , and this is a range in the first composition hard coating film that runs toward the surface of the first composition hard coating film starting from the interface 6.
  • the multilayer film-coating member is characterized in that the oxygen content of the first composition hard coating film within that range is limited to a range of less than 5 atm.%.
  • Other examples of the coating film structure are shown in Fig. 2 and Fig. 3 .
  • the second composition hard coating film has a double-layer structure; and in Fig. 3 , the first composition hard coating layer has a double-layer structure.
  • the invention may be mentioned in which both the first composition hard coating layer and the second composition hard coating layer have a double-layer structure.
  • the ratio of the peak area X of B-O to the peak area Y of B-N, X/Y, as obtained from the peak separation of the 1s orbit of B in X-ray photoelectric spectrometry may be X/Y ⁇ 0.2.
  • the ratio limitation is because, when a large quantity of B oxide exists near the interface, then the reduction in the adhesion strength is remarkable, and therefore, the presence of B oxide in the interface must be limited to less than a predetermined level.
  • the multilayer film-coated member that is coated with hard coating films of the invention may have improved heat resistance of the coating films and may prevent the member from being abraded more by temperature elevation, and in addition, the lubricative characteristics of the multilayer coating film of the member can be improved therefore preventing the adhesion of work materials to the cutting tools.
  • the most characteristic feature of the invention is that the multilayer film-coated member may have significantly improved adhesion strength while still having the above-mentioned characteristics as such. Because of this effect, the coating film may exhibit its excellent capability stably for a long period of time. The effect of the invention in practical use is demonstrated in coating of cutting tools.
  • the cutting tools coated according to the invention may exhibit excellent heat resistance and abrasion resistance with the excellent adhesion strength of the coating films kept ensured as such, and therefore, they may be applicable to high-speed and rapid-feed cutting work.
  • the multilayer film-coated member of the invention having excellent adhesion strength and excellent lubricity may evade such accidents.
  • the method for producing the multilayer film-coated member of the invention is favorable for forming the coating film having the above-mentioned characteristics.
  • the constitution of the hard coating film 1 of the invention comprises a second composition hard coating film 3 and a first composition hard coating film 4 as formed on the surface of a substrate 2.
  • the thickness of the second composition hard coating film may be from 100 nm to less than 5000 nm, more preferably from 100 nm to less than 3000 nm.
  • the thickness of the first composition hard coating film may be from 10 nm to less than 1000 nm, more preferably from 40 nm to less than 600 nm.
  • the main role of the second composition hard coating film in the invention is to act as assistance for the first composition hard coating film so that the first film may sufficiently exhibit its advantages of abrasion resistance and heat resistance.
  • the ratio of the film thickness of the first composition hard coating film to the overall film thickness could not increase from the viewpoint of the residual compression stress of the film, and in such a case, the second composition hard coating film is made thick.
  • a preferred thickness ratio of the first composition hard coating film and the second composition hard coating film is such that, when the overall thickness is considered 100, the ratio of the first composition hard coating film is from 2 % to 50 %.
  • the adhesion strength of the second composition hard coating film to the substrate surface, and the hardness and the residual compression stress thereof are important factors.
  • the substrate 2 may be any of cemented carbide, cermet, high-speed steel, sintered boron nitride, ceramics, mold steel, heat-resistant alloy.
  • the cutting tools are, for example, end mill, drill, reamer, broach, hob cutter, microdrill, router, milling insert, turning insert.
  • the heat-resistant alloy includes titanium alloy, Inconel, aluminium alloy.
  • the first composition hard coating film in the invention comprises Si, B, C, N and O as the indispensable ingredients so as to satisfy its characteristics of abrasion resistance and heat resistance.
  • Si, B and C are elements that readily form oxides. Therefore, the coating film may readily take thereinto the impurity oxygen in the chamber of coating machine or in a process gas and the oxides in the surface of a coating target.
  • highly purified gases to reduce the amount of oxygen of the process gases within the chamber.
  • the adhesion strength may greatly lower.
  • the oxide take-in amount in the initial stage in the film formation of the first composition hard coating film must be controlled.
  • Si and B oxides have significant influences on the reduction of the adhesion strength of the film.
  • a typical oxide of Si, SiO 2 is stable up to 1700°C or so; but a typical oxide of B, B 2 O 3 liquefies at 500°C or so, as is known from the B 2 O 3 -SiO 2 binary phase diagram of Fig. 4 .
  • SiO 2 and B 2 O 3 undergo eutectic reaction, and form a eutectic flux at about 450°C.
  • flux may be formed to lower the adhesion strength.
  • the first composition hard coating film it is important to control the substrate temperature so as not to be higher than the eutectic temperature of SiO 2 and B 2 O 3 .
  • the film formation is attained with monitoring the temperature of the substrate, and the film-forming temperature is so controlled that the substrate temperature may be not higher than 400°C.
  • the second composition hard coating film it may be unnecessary to control the substrate temperature to 400°C or lower; however, special attention should be paid so that the substrate temperature in the initial stage in the film formation of the first composition hard coating film could be not higher than 400°C. Oxygen adhering to the target surface may be taken into the film, and therefore, it is desirable to clean the target surface by preliminary discharging. Combining the temperature control and the preliminary discharging is more preferred. Since the first composition hard coating film may readily take oxygen thereinto in the initial stage of the film formation, the RF sputtering output power in the preliminary discharging is desirably a relatively high output power of from 500 W to 2500 W or so, and this may be effective for preventing the film from taking oxygen therein. According to the method as above, the requirement can be satisfied that the oxygen content in the range of the film of at least 500 nm from the interface is limited to a range of less than 5 atm.%.
  • the ratio of the peak area X of B-O to the peak area Y of B-N, X/Y, as obtained from the peak separation of the 1s orbit of B in X-ray photoelectric spectrometry may satisfy X/Y ⁇ 0.2, thereby further bettering the adhesion strength of the film.
  • the computation method is as follows: The peak of the 1s orbit of B is subjected to peak separation into the peak of B-O and that of B-N, and the individual peak areas X and Y are computed.
  • the peak area ratio of B-O to B-N, X/Y is computed.
  • the ratio X/Y could be at most 0.2, it is important that the film does not take oxygen thereinto. Accordingly, for example, the film formation is attained with controlling the film-forming temperature, and it is necessary to control the film-forming temperature so that the substrate temperature could be not higher than 400°C. Oxygen adhering to the target surface may be taken into the film, and therefore, it is desirable to clean the target surface by preliminary discharging. Combining the temperature control and the preliminary discharging is more preferred.
  • the RF sputtering output power in the preliminary discharging is desirably a relatively high output power of from 500 W to 2500 W or so, and in the initial stage of the film formation after this, it is necessary that the film formation is initiated at a low output power of 100 W or so (the film-forming speed is not higher than 0.25 nm/hr).
  • the first composition hard coating film in the invention is represented by Si a B b N c C d O e , comprising Si, B, C, N and O as the indispensable ingredients.
  • B, C and N are the ingredients effective for increasing the hardness and improving the heat resistance and the lubricity of the hard coating film.
  • O is the ingredient effective for improving the lubricity and the heat resistance of the film.
  • the value b that indicates the B content is 0.01 ⁇ b ⁇ 0.2.
  • the hardness and the heat resistance of the film are insufficient, and the film is too brittle with the result that the film may be delaminated and its cutting performance could not be improved.
  • b is at least 0.01 in the definition thereof mentioned above.
  • B is effective for improving the lubricity characteristic of the film.
  • B may readily react with oxygen, and therefore, if too much B is added to the film, it may worsen the film characteristics and the film adhesion strength.
  • Adding both Si and B to the film improves both the hardness and the heat resistance of the film. This is especially remarkable when Si exists as its boride.
  • the value c that indicates the N content is 0.05 ⁇ c ⁇ 0.6.
  • the value d that indicates the C content is 0.1 ⁇ d ⁇ 0.7.
  • the content of O is 0 ⁇ e ⁇ 0.2.
  • the film readily take oxygen therein, and the film always contains oxygen as an impurity, and therefore as its definition, e is more than 0.
  • oxygen diffusion in the film may be reduced in abrasive environments, and therefore the oxidation resistance of the film even at high temperatures may be improved.
  • the O content profile in the film is preferably such that the oxygen content is the highest in the vicinity of the surface layer within a range of from the uppermost surface of the hard coating film toward a depth of less than 500 nm in the film thickness direction, from the viewpoint of the lubricity of the film in abrasive environments.
  • oxygen exists in the film as oxides of silicon (Si) and boron (B).
  • Si silicon
  • B boron
  • oxygen exists in the film as its solution solid, then it forms a Si oxide and a B oxide with the increase in the cutting temperature during cutting work.
  • the components of the object being cut may diffuse inside the coating film, thereby causing film fusion, and the mechanical characteristics of the coating film may be thereby worsened. Accordingly, it is desirable that oxygen exists in the coating film as previously formed oxides.
  • the multilayer film-coated member of the invention can exhibit excellent abrasion resistance and heat resistance for a long period of time even in abrasive environments where the temperature rises owing to the increase in the cutting speed and to the increase in the hardness of the objects to be cut.
  • the first composition hard coating film has extremely excellent heat resistance, and in environments where the temperature rises, it especially exhibits its effect.
  • the main reason is because the first composition hard coating film has a low friction coefficient in high-temperature environments, and therefore it extremely reduces the thermal influence on the substrate.
  • the reason why the friction coefficient of the film is especially low in high-temperature environments is because SiO 2 and B 2 O 3 are formed in abrasive environments.
  • SiO 2 and B 2 O 3 form a liquid phase containing SiO 2 and B 2 O 3 at a low temperature of 450°C or so.
  • the first film is at least combined with the second composition hard coating film to be described below, or it is in the form of a multilayer hard coating film containing the second composition hard coating film.
  • the multilayer film-coated member of the invention is a concept that contains an interlayer to be described below.
  • the main role of the second composition hard coating film in the invention is that it exists so that the first composition hard coating film may sufficiently exhibit its effect.
  • the second composition hard coating film exhibits excellent adhesion strength and abrasion resistance in practical use.
  • the second composition hard coating film contains Si, its atomic ratio must be less than 0.5 to the metal element of 1.0, and thus, the second film is differentiated from the first composition hard coating film.
  • the multilayer hard coating film that comprises the first composition hard coating film and the second composition hard coating film exhibits its effect of adhesion strength and abrasion resistance.
  • the second composition hard coating film may have a double-layered structure of, for example, (TiAl)N/(TiSi)N as in Fig. 2 .
  • the abrasion resistance and the adhesiveness of the multilayer film are much improved.
  • the ratio of the first composition hard coating film to the overall multilayer hard coating film could not be increased from the viewpoint of the residual compression stress, and in such a case, the second composition hard coating film is made thick.
  • a preferred thickness ratio of the first composition hard coating film and the second composition hard coating film is such that, when the overall thickness is considered 100, the ratio of the first composition hard coating film is from 2 % to 50 %.
  • compositions of the second composition hard coating film are (AlTi)N, (AlCr)N, (AlCrSi)N, (TiSi)N, (AlTiSi)N, from the viewpoint of the adhesion strength to the substrate and the adhesion strength to the first composition hard coating film.
  • compositions of the second composition hard coating film as combined with the interlayer are (TiAl)N/(TiSi)N, (AlCrSi)N/(TiSi)N, (TiAl)N/(CrSi)BN.
  • a sputtering method (hereinafter this may be referred to as "SP method") is effective that uses a composite target containing silicon carbide and boron nitride.
  • SP method a sputtering method
  • a composite target containing silicon carbide and boron nitride is preferably used; however, silicon carbide and boron nitride may be put on different evaporation sources and they may be sputtered simultaneously to produce the intended object.
  • the first composition hard coating film is formed according to an SP method
  • the second composition hard coating film is formed according to an arc ion plating method (hereinafter this may be referred to as "AIP method") and/or an SP method.
  • AIP method an arc ion plating method
  • an SP method it is important to improve the adhesion strength between the second composition hard coating film 3 and the substrate 2, and therefore an AIP method is suitable to the boundary between the second composition hard coating film 3 and the substrate 2.
  • coating according to an SP method may be effective for improving the abrasion resistance.
  • the SP method may be combined with an AIP method.
  • the first composition hard coating film 4 may be coated according to an SP method.
  • the power in the SP method and the AIP method for the coating may be a high-frequency power or a direct current power; but from the viewpoint of the stability in the coating process, the sputtering power source is preferably a high-frequency power.
  • a high-frequency bias power source is more preferred in consideration of the electronic conductivity of the hard coating film and the mechanical characteristics of the hard coating film.
  • the multilayer coating film of the invention may remarkably exhibit its effect and may improve the abrasion resistance of the tools even in severe abrasive environments.
  • FIG. 5 schematically shows the structure of coating machine 16 for carrying out the method of the invention.
  • the coating machine 16 comprises a vacuum chamber 13, four types of coating sources 8, 9, 10 and 11 as targets, and their shutters 17, 18, 19 and 20.
  • 8 and 10 are RF-coating sources; and 9 and 11 are arc sources.
  • the coating sources are individually shut off by the shutters 17, 18, 19 and 20. Thus acting independently of each other, the individual coating sources may be separately shut off. Accordingly, it is unnecessary to stop the coating sources during the coating operation.
  • Argon as a process gas and N 2 , O 2 and C 2 H 2 as reaction gases are fed into the vacuum chamber 13, for which the chamber has a vapor duct 15 equipped with a switch.
  • the substrate holder 14 is provided with a rotary mechanism, and this is connected to a DC bias power or RF bias power 12.
  • a hard coating film was formed according to the following coating method.
  • the first coating method comprises a first step of heating a tool at 500°C, a second step of ion cleaning for about 30 minutes by applying a pulse bias voltage having a negative voltage of 200 V, a positive voltage of 30 V, a frequency of 20 kHz and a pulse/pose 4 ratio of, a third step of coating with (AlTi)N by an arc source, a fourth step of coating with (AlTi)N by an arc source and washing the target surface by discharging the sputtering target while the shutter is shut, a fifth step of coating with SiBNCO by using a target having a molar blend ratio, BN/SiC of 1/3 in a mode of RF sputtering with an RF-coating source, and a sixth step of coating with SiBNCO by RF + DC by applying a DC bias having a negative voltage of 50 V, in addition to the RF bias.
  • the coating was attained through the above lst to 6th steps. Finally, a laminate structure of (AlTi) N and SiBNCO laminated in that order was formed, and the film thickness was about 3 ⁇ m. In the RF sputtering, the temperature inside the chamber was so controlled that the tool temperature could be not higher than 400°C.
  • the sample coated according to the first coating method is referred to as a sample 1 of the invention.
  • the second coating method is as follows: In RF sputtering, oxygen gas was used as the reaction gas.
  • the sample coated according to the second coating method is referred to as a sample 25 according to the invention.
  • a sample 16 according to the invention was produced.
  • the third coating method is as follows : In RF sputtering, used was a target having a molar blend ratio, BN/SiC of 1/1 as an RF coating source.
  • the sample coated according to the third coating method is a sample 18 according to the invention.
  • the samples 2 to 10 and the samples 14 to 22 of the invention differ in the second composition hard coating film.
  • nitrogen, oxygen or acetylene, respectively was used as the reaction gas in forming the surface layer to be the outer layer of the SiBNCO film.
  • the temperature inside the chamber was so controlled that the tool temperature could be not lower than 500°C.
  • the fourth coating method is as follows: A second composition hard coating film was formed according to a DC sputtering method, and the first composition hard coating film was formed according to an RF sputtering method.
  • the samples produced according to the fourth coating method are referred to as samples 23 and 24 of the invention.
  • Tables 1, 2 and 3 The details of the samples are shown in Tables 1, 2 and 3.
  • EPMA electron probe microanalyzer
  • AES Auger electronic spectrometry
  • the depth was computed on the basis of the etching rate of SiO 2 . Additional examples for second hard coating films can be found following Table 1.
  • a second composition hard coating film may also include Ni, Ce, or Mg forming among others for example chemical compositions like Ti a Si b Ce c , in particular for example Ti 0.9 Si 0.09 Ce 0.01 N or Al 0.66 Cr 0.30 Mg 0.02 Si 0.02 N or Cr 0.84 Ni 0.1 B 0.05 Si 0.01 ⁇ Table 2 - Oxygen Content (atm.%) Profile from Interface in Sample Sample No Distance from interface (nm) 0 25 100 200 300 400 500 600 700 800 900 1 2.6 3.0 2.9 2.7 2.3 2.2 2.2 2.2 2.1 2.1 2.1 2 2.8 2.9 2.9 2.8 2.6 2.5 2.5 2.4 2.4 2.4 2.4 3 2.8 2.8 2.7 2.7 2.7 2.7 2.6 2.6 2.6 4 2.7 2.8 2.7 2.7 2.7 2.7 2.6 2.6 2.5 2.5 2.5 5 2.8 2.9 2.9 2.8 2.7 2.7 2.7 2.6 2.6 2.6 2.6 2.6 2.5 2.5 2.5 5 2.8 2.9 2.9 2.8 2.7 2.7 2.7 2.6 2.6 2.6
  • the chemical elements are subdivided into two groups of chemical elements.
  • Group G consists of chemical elements G i , which are B, N, O, C, or S.
  • Group M consists of all other chemical elements M i used in the second composition hard coating layer. That is group M includes in particular the chemical elements M i which are Al, Ti, Cr, Ni, Ce, Mg, Nb, W, Si, V, Zr and Mo.
  • all chemical formulae characterizing the composition hard coating film have the following form:
  • Sample No. 20 is characterized by the chemical formula: (Cr 0.9 Si 0.1 )BNO consisting of the group M elements M i which are in this example Cr and Si and further consisting of group G elements G i which are in the present example of sample No. 20 B, N, and O, wherein (Cr 0.9 Si 0.1 )BNO in the scope of the present invention means (Cr 0.9 Si 0.1 ) X (BNO) 1-X with 0.4 ⁇ X ⁇ 0.6 , as generally defined above by the expression (Group M elements) x (Group G elements) 1-X with 0.4 ⁇ X ⁇ 0.6.
  • the film surface of Examples, Comparative Examples and Conventional Examples was tested according to a Rockwell dent test (pressure probe: Rockwell C scale, pressing load: 150 kgf), and from the condition of the coating film around the dented area, the samples were evaluated for the adhesiveness according to the following criteria.
  • the results are shown in Table 3 as four ranks of from A to D.
  • the adhesion strength is A > B > C > D; and A is the best.
  • the samples 1 to 24 of the invention had good adhesion strength.
  • the samples 2 and 9 of the invention differ from the sample 1 of the invention in point of the composition of the second composition hard coating film.
  • the sample 12 of the invention was formed with adding oxygen as the reaction gas in forming the surface layer of the first composition hard coating film. In this, no oxygen was used in forming the interface and around it, in which the oxygen content was controlled, therefore having no influence on the adhesiveness.
  • the oxygen content within the range of from the interface to 600 nm is not more than 5 atm.%, and the oxygen content in the range of 700 nm or more is over 5 atm.%; but the adhesion strength is good.
  • the oxygen content in the other area has no problem.
  • the oxygen content in a range of from the interface to 400 nm is more than 5 atm.%
  • the oxygen content in a range of 500 nm or more is not more than 5 atm.%; but the adhesion strength is not good. It is known that, when the oxygen content within a range of from the interface to 500 nm is more than 5 atm% even once, the adhesion strength is not good.
  • the oxygen content in a range of from the interface to 500 nm is slightly more than 5 atm.%, and therefore, the adhesion strength is not good.
  • the oxygen content in the conventional samples 38 and 39 is more than 5 atm.% within the entire region, and therefore the adhesion strength is not good. From these results, it is confirmed that the specific limitation of the oxygen content in the first composition hard coating film within a range of at least 500 nm from the interface of the first composition hard coating film on the side of the substrate, to less than 5 atm.% improves the adhesion strength.
  • Table 3 shows the ratio of the B-O peak area X to the B-N peak area Y, X/Y, as obtained from the peak separation of the 1s orbit of B in X-ray photoelectric spectrometry.
  • the comparative samples 25 and 26 and the conventional samples 27 and 28 do not satisfy X/Y ⁇ 0.2, and contain a large quantity of B oxide, and therefore their adhesion strength is insufficient. In the Rockwell dent test, the samples showed film peeling.
  • the samples of the invention all satisfy X/Y ⁇ 0.2 and B oxide is reduced therein, and therefore, the samples have sufficient adhesion strength and did not show film peeling.
  • a second composition hard coating film 3 was deposited onto the substrate 2 using an arc coating technique.
  • the thickness of this second composition hard coating film is between 0.5 ⁇ m and 10 ⁇ m and is preferably about 1 ⁇ m.
  • an alternating sequence of first composition hard coating layers 4 and second composition hard coating 3 layers was then coated onto the second composition hard coating film 3 as which was first directly coated onto the substrate 2.
  • the thickness of a single layer of the sequence of the first and second composition hard coating films 3,4 is between 2.5nm and 100nm, wherein the sequence of the first and the second composition hard coating films 3,4 may comprise a considerable number of single layers, for example up to 10 layers, or up to 50 to 100 layers or up to 1000 layers or in special cases more than 1000 single layers. Accordingly the thickness of the entire sequence of single layers is for example between 0.5 ⁇ m and 10 ⁇ m and is in a special embodiment of the present invention about 1 ⁇ m.
  • a sequence of a plurality of different first composition hard coating films 4 is provided as a top layer.
  • the entire thickness of the sequence of different first composition hard coating films 4 can be between 10nm and 2000nm, preferably between 20nm and 100nm.
  • the thickness of a single first composition hard coating film 4 of the top layer is preferably between 2.nm and 100nm.
  • the single layers of first composition hard coating films 4 of the top layer may differ with respect to their chemical composition, for example with respect to the oxygen content or an other chemical component. That is the a/b ratio and or the x/y ratio may vary from one single first composition hard coating film 4 to another one.
  • the chemical composition of the first composition hard coating films of the intermediate layers and the chemical composition of the second composition hard coating films 3 may vary from one single layer of the intermediate layer to another one.
  • one single second composition hard 3 coating film may be a TiSiCeN-film 3 and another single second composition hard coating film 3 can be a AlCoSN-film 3.
  • the first composition hard coating films 4 are deposited by using a sputter process wherein the second composition hard coating films 3 are produced using an arc technique.

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  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)

Claims (14)

  1. Elément revêtu d'un film multicouche fabriqué par le revêtement de la surface d'un substrat avec au moins deux films de revêtement dur ayant des compositions différentes, où le film dur de la première composition de la couche la plus extérieure des films de revêtement dur représenté par SiaBbNcCdOe avec a+b+c+d+e=1, 0,1 ≤ a ≤ 0,5, 0,01 ≤ b ≤ 0,2, 0,05 ≤ c ≤ 0,6, 0,1 ≤ d ≤ 0,7 et 0 < e ≤ 0,2, le film de revêtement dur de la deuxième composition de la couche inférieure en dessous du film de revêtement dur de la première composition est un film dur ayant au moins deux sélectionnés parmi Al, Ti, Cr, Ni, Ce, Mg, Nb, W, Si, V, Zr et Mo et au moins un sélectionné parmi N, B, C, O et S, et la teneur en oxygène du film dans une plage d'au moins 25 nm de l'interface du film de revêtement dur de la première composition qui est en contact avec la couche située en dessous vers la surface du film de revêtement dur de la première composition est limitée à une plage inférieure à 3,5 atm.%.
  2. Elément revêtu d'un film multicouche selon la revendication 1, dans lequel la teneur en oxygène du film dans une plage d'au moins 100nm, en particulier 300nm, de préférence 500nm depuis l'interface du film de revêtement dur de la première composition qui est en contact avec la couche située en dessous vers la surface du film de revêtement dur de la première composition est limitée à une plage inférieure à 4 atm%.
  3. Elément revêtu d'un film multicouche selon la revendication 1 ou 2, dans lequel le rapport de la zone de crête X de B-O à la zone de crête Y de B-N, X/Y, comme obtenu par la séparation de la crête de l'orbite 1s de B en spectrométrie photoélectrique à rayons X, est de X/Y ≤ 0,2, dans une plage d'au moins 500 nm depuis l'interface du film de revêtement dur de la première composition qui est en contact avec la couche située en dessous vers la surface du film de revêtement dur de la première composition.
  4. Elément revêtu d'un film multicouche selon l'une quelconque des revendications précédentes, dans lequel l'épaisseur du film de revêtement dur de la deuxième composition est de 100nm à moins que 5000nm, de préférence de 100nm à moins que 3000nm.
  5. Elément revêtu d'un film multicouche selon l'une quelconque des revendications précédentes, dans lequel, lorsque l'épaisseur d'ensemble est considérée comme étant 100, le rapport du film de revêtement dur de la première composition est de 2% à 50%.
  6. Elément revêtu d'un film multicouche selon l'une quelconque des revendications précédentes, où 0,05 < b 0,2.
  7. Elément revêtu d'un film multicouche selon l'une quelconque des revendications précédentes, dans lequel 0,1 < c 0,35.
  8. Elément revêtu d'un film multicouche selon l'une quelconque des revendications précédentes, dans lequel 0,15 < d 0,4.
  9. Elément revêtu d'un film multicouche selon l'une quelconque des revendications précédentes, dans lequel 0,01 <e < 0,15.
  10. Elément revêtu d'un film multicouche selon l'une quelconque des revendications précédentes, dans lequel le film de revêtement dur de la deuxième composition possède une structure à couche double en particulier en (TiAl)N /(TiSi) N.
  11. Elément revêtu d'un film selon l'une quelconque des revendications précédentes, dans lequel la composition du film de revêtement dur de la deuxième composition est (AlTi)N et/ou (AlCr)N et/ou (AlCrSi)N et/ou (TiSi)N et/ou (AlTiSi), en particulier pour améliorer la force d'adhérence au substrat et/ou au film de revêtement dur de la première composition.
  12. Elément revêtu d'un film multicouche selon l'une quelconque des revendications précédentes, dans lequel en combinaison avec une intercouche, une composition du film de revêtement dur de la deuxième composition est (AlCrSi)N/(TiSi)N et/ou (TiAl)N/CrSi)BN.
  13. Procédé de production d'un élément revêtu d'un film multicouche en accord avec l'une quelconque des revendications précédentes, dans lequel le film de revêtement dur de la première composition est formé sous une commande de température pour maintenir la température du substrat à un niveau qui n'est pas plus élevé que 400°C, et après que la surface cible de revêtement a été nettoyée par une décharge préliminaire, le film est formé à une puissance de sortie de pulvérisation cathodique inférieure à 2500 W jusqu'à une épaisseur d'au moins 5 nm depuis l'interface à la couche située en dessous.
  14. Un outil de coupe, un moule et un moteur à combustion ou un élément nécessitant une résistance à la chaleur et une résistance à l'abrasion pour des aéronefs, des turbines au sol, des moteurs, des garnitures d'étanchéité, des engrenages, des pistons ayant un élément revêtu d'un film multicouche selon l'une quelconque des revendications 1 à 12, produit en utilisant un procédé en accord avec la revendication 13.
EP09159721A 2008-07-31 2009-05-08 Élément revêtu de film multicouches et son procédé de production Active EP2149624B1 (fr)

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US8911867B2 (en) * 2009-06-18 2014-12-16 Oerlikon Metaplas Gmbh Protective coating, a coated member having a protective coating as well as method for producing a protective coating
CN102234758B (zh) * 2011-04-20 2013-04-17 浙江省平湖市工具厂 涂钛丝锥的加工工艺
CN102758188A (zh) * 2011-04-28 2012-10-31 鸿富锦精密工业（深圳）有限公司 镀膜件及其制造方法
IN2014CN04404A (fr) * 2011-12-15 2015-09-04 Kobe Steel Ltd
CN104988461A (zh) * 2015-07-31 2015-10-21 宁波威霖住宅设施有限公司 一种铁基材表面高防腐的处理方法
JP6577036B2 (ja) 2015-09-04 2019-09-18 オーエスジー株式会社 硬質被膜および硬質被膜被覆部材
JP6421733B2 (ja) * 2015-09-30 2018-11-14 三菱日立ツール株式会社 硬質皮膜、硬質皮膜被覆部材、及びそれらの製造方法
US10170321B2 (en) 2017-03-17 2019-01-01 Applied Materials, Inc. Aluminum content control of TiAIN films
US10478347B2 (en) * 2017-06-21 2019-11-19 The Procter & Gamble Company Nozzle assembly used to manufacture absorbent articles
JP6963932B2 (ja) * 2017-08-14 2021-11-10 Ｄｏｗａサーモテック株式会社 珪炭窒化バナジウム膜、珪炭窒化バナジウム膜被覆部材およびその製造方法
GB201802468D0 (en) 2018-02-15 2018-04-04 Rolls Royce Plc Coated substrate

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EP0999290B1 (fr) * 1998-10-27 2005-03-23 Mitsubishi Materials Kobe Tools Corporation Elément revêtu résistant à l'usure
JP3084402B1 (ja) * 1999-04-14 2000-09-04 工業技術院長 ＡｌＴｉ系合金スパッタリングターゲット及び耐摩耗性ＡｌＴｉ系合金硬質皮膜並びに同皮膜の形成方法
JP3370291B2 (ja) 1999-04-27 2003-01-27 独立行政法人産業技術総合研究所 耐熱硬質被膜被覆工具
JP3417907B2 (ja) * 2000-07-13 2003-06-16 日立ツール株式会社 多層皮膜被覆工具
JP2002087896A (ja) 2000-09-12 2002-03-27 Mitsubishi Heavy Ind Ltd 自己修復性高耐熱耐酸化性皮膜及び積層体
EP1422311B1 (fr) * 2002-11-19 2007-02-28 Hitachi Tool Engineering Ltd. Couche dure et outil revêtu d'une telle couche dure
JP2005271190A (ja) * 2003-12-05 2005-10-06 Sumitomo Electric Hardmetal Corp 表面被覆切削工具
US7348074B2 (en) * 2005-04-01 2008-03-25 Oc Oerlikon Balzers Ag Multilayer hard coating for tools
JP4672442B2 (ja) * 2005-05-31 2011-04-20 オーエスジー株式会社 硬質積層被膜、および硬質積層被膜被覆工具
JP4380622B2 (ja) 2005-11-04 2009-12-09 日立ツール株式会社 多層皮膜被覆部材及びその製造方法
EP1783245B1 (fr) * 2005-11-04 2018-01-24 Oerlikon Surface Solutions AG, Pfäffikon Outil ou pièce d'usure et procédéde pvd pour déposer un revêtement à la surface d'un outil ou d'un pièce d'usure

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EP2149624A1 (fr) 2010-02-03
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